JPH04185773A - Processing of cellulosic fiber for preventing staining with fluorescent dye - Google Patents

Abstract

PURPOSE:To enable the subject stain-proofing treatment while keeping the softness and preventing the lowering of the strength of the fiber by carboxylating a cellulosic fiber at a specific ratio with a treating agent containing monochloroacetic acid or its salt and sodium hydroxide, and crosslinking with a resin reactive with cellulose. CONSTITUTION:A cellulosic fiber is carboxymethylated by conventional method using a treating agent containing monochloroacetic acid or its Na salt and sodium hydroxide. The carboxylation ratio is 0.05-8mol% based on the cellulose molecule. The treated fiber is added with 1-4wt.% (in terms of solid, based on the fiber) with an N-methylol cellulose-reactive resin and crosslinked by heat-treatment to obtain a cellulosic fiber resistant to staining with fluorescent dye in the case of washing with a detergent containing a fluorescent dye.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a fluorescent dye stain prevention processing method that prevents fluorescent dye staining when cellulose fibers are washed with a fluorescent dye-containing detergent. It is.

(Prior Art) As a processing method to prevent cellulose fibers from being contaminated by fluorescent dyes when they are washed with fluorescent dye-containing detergents, fluorescence suppressants and N-methylol-based cellulose-reactive types have been conventionally used. The method used was to apply a treatment solution containing resin and catalyst and then perform dry heat treatment, but since the fluorescence suppressor is a cationic, light brown coloring solution, the fabric to be processed tends to discolor and become dull.

The stain prevention effect of fluorescent dyes was also not sufficient. In order to obtain sufficient fluorescent dye stain prevention processing effect.

It is necessary to directly use the N.methylol-based cellulose-reactive resin at a high concentration, and in this case there is a drawback that the tear strength is greatly reduced.

Another method is to use monochloroacetic acid or sodium monochloroacetate and caustic soda to anionize cellulose by carboxymethylating it, but this method does not have a sufficient fluorescent dye stain prevention effect. If carboxymethylation is obtained, the fabric becomes slimy and uncomfortable when wet, and when dried, the texture hardens like glue.

(Problems to be Solved by the Invention) The present invention was made in view of the current situation, and provides cellulose fibers with excellent fluorescent dye stain prevention performance while suppressing hardening of texture and decrease in strength. The purpose is to obtain a processing method that

(Means for Solving the Problems) The present invention achieves the above object and has the following configuration.

That is, 1 the present invention treats cellulose fibers with a treatment solution containing monochloroacetic acid or sodium monochloroacetate and caustic soda to reduce the cellulose molecules to 0.
, 05 to 8 mo]% carboxymethylated, and then a crosslinking reaction is carried out by applying 1 to 4% of the solid content of N-methylol cellulose-reactive resin based on the weight of the fiber. The gist of this paper is a processing method for preventing fluorescent dye staining.

The present invention will be explained in detail below.

The cellulose fiber applied to the present invention is cotton.

Linen, rayon, etc., and a blend of these fibers with synthetic fibers or protein fibers such as 1M wool.

Composite materials such as intertwisted and interwoven materials are also included. in this case.

It is desirable that cellulose fibers be contained in an amount of at least 30%. Further, the cellulose fiber may be in the form of a single thread or a fabric such as a woven or knitted fabric.

In the method of the present invention, first, the above-mentioned cellulose fiber is carboxymethylated by 0.05 to 3 rno1% of its cellulose molecules using a treatment liquid containing monochloroacetic acid (M4) or monochloroacetic acid (M4), and caustic soda.

Carboxymethylation is carried out using monochloroacetic acid or monochloroacetic acid), but if the carboxymethylation is less than 3 mo1% of the cellulose molecule, the cellulose-reactive resin described below may not penetrate into the inside of the fiber. << Also, if it exceeds 8 mol %, the fiber will become coarsely hardened or its tenacity will decrease, which is inappropriate.

For the carboxymethylation treatment, either a dipping method or a dry heat treatment method may be employed. In the immersion method, 2 to 1
After applying a 0%, preferably 3 to 7% aqueous solution of caustic soda, the mixture is squeezed using a mangle.

2. Without drying, immerse in a 2-15%, preferably 3-10%, monochloroacetic acid or sodium monochloroacetic acid aqueous solution. After treatment, it was first neutralized with acetic acid.

Complete carboxymethylation. In the dry heat treatment method.

After applying a caustic soda solution with the same concentration as in the above-mentioned dipping method, the liquid was squeezed out using a mangle, and then an IJium aqueous solution was applied and the liquid was squeezed out with a mangle. Carboxymethylation is performed by dry heat treatment, and the treatment is completed by neutralization in the same manner. Monochloroacetic acid or sodium monochloroacetate and sodium chloride can also be treated in the same bath. In this case, a treatment liquid is applied, squeezed with a mangle, and then subjected to dry heat treatment, followed by neutralization in the same manner to complete carboxymethylation.

After carboxymethylation 9 In the present invention, the solid content of the N-methylol-based cellulose-reactive resin is 1 to 1 to the fiber weight.
Add 4% and perform a crosslinking reaction.

As the N/methylo-fiber-reactive resin used in the crosslinking reaction of the present invention, dimethylol ethylene urea resin, dimethylol dihydroxy ethylene urea resin, dimethylol dihydroxy ethylene urea resin, etc. can be used. These resins contain magnesium chloride, zinc chloride, and
A metal salt acidic catalyst such as zinc nitrate is used in combination.

Dispersed N-methylol-based cellulose-reactive resins, which are suitable for crosslinking, are commercially available for use in fiber processing.

For example, N-methylol-based cellulose-reactive resin.

Sumitex Resin 901. Sumitex Resin N5-
11. Examples include Sumitex Resin 81.0 (all manufactured by Sumitomo Chemical). As the metal salt acidic catalyst, Sumitex Accelerator-X-80° Sumitex Accelerator-KX, Sumitex Accelerator-χ-11
0 (all manufactured by Sumitomo Chemical ■), etc.

The amount of the N-methylol-based cellulose-reactive resin used for crosslinking is suitably 1 to 4% based on the weight of the fiber as a solid content, but 2 to 3% is usually preferred. If the amount used is less than 1%, the effect of preventing fluorescent dye staining of the present invention cannot be obtained, and if it exceeds 4%, the strength of the cellulose fiber will be significantly reduced, which is inappropriate light.

The metal salt acidic catalyst to be used in combination with the N-methylol cellulose-reactive resin is suitably 10 to 15% by weight based on the resin, but the amount used may vary depending on the activity of the catalyst used. When processing the N-methylol-based cellulose-reactive resin, a softening agent may be used in combination depending on the desired texture.

In the crosslinking reaction, after applying the resin liquid, drying
This can be carried out by dry heat treatment at ℃ for 1 to 3 minutes.

By the above method, it is possible to obtain a cellulosic fiber fabric with little fluorescent dye staining even when washed using a detergent containing fluorescent dye.

The invention consists of one or more configurations.

(Function) When cellulose fibers are slightly carboxymethylated as in the method of the present invention, the degree of crystallinity of cellulose decreases within a range that does not cause any practical problems, and in such a state, N-methylol cellulose When a reactive resin treatment is performed, even a small amount of the resin uniformly penetrates into the interior of the cellulose fibers and causes a crosslinking reaction.

This crosslinking reaction suppresses the affinity with fluorescent dyes even to the inside of the fibers, and as a result, it becomes possible to obtain a stain-preventing effect against fluorescent dyes contained in detergents during washing. Furthermore, since the decrease in the crystallinity of cellulose during carboxymethylation is of such a degree that it does not pose a practical problem, the strength of the cellulose fibers is also maintained within a practically effective range. Furthermore, since carboxymethylation is limited to a mild level, hardening of the cellulose fibers is suppressed and a soft texture can be obtained.

(Example) Next, the present invention will be explained in more detail with reference to an example, in which the performance of the fabric in the example was measured.

The evaluation was performed using the following method.

(1), fluorescent white skin Using a Model 139 spectrophotometer (Hitachi).

Measurement was performed at a wavelength of 432 nm.

(2) Tear strength Measured according to JIS L-1096 (Pensulam method).

(3) Texture The following three-level evaluation was performed by a sensory test.

○: Flexible △: Normal ×: Hard (4) Washing test method According to JIS L-0217 (103 method).

Wash 2Ω times.

Example 1 A cotton fabric with a wire number of 60 (warp density 100 fibers/inch, weft density 95 fibers/inch) was subjected to yarn burning, desizing, scouring, bleaching, and mercerization as a workpiece fabric. This was impregnated with a treatment solution of the following formulation.

After squeezing the liquid with a mangle at a squeezing rate of 70%, it was dried at 100°C for 2 minutes.

[Prescription 1] Lithium monochloroacetate 1. OOg/R caustic soda (flake) 50g/12 Next, neutralize with 1 g/I of glacial acetic acid at 40°C for 3 minutes, followed by
After soaping with 1 g/R of Actinol R-100 (manufactured by Matsumoto Yushi Co., Ltd., a nonionic surfactant) at 90° C. for 3 minutes, the sample was dried to complete carboxymethylation. The degree of carboxymethylation at this time was 4 mo1%.

Thereafter, it was impregnated with a treatment liquid of the following formulation 2, and after squeezing with a mangle at a squeezing rate of 70%, it was dried at 110°C for 2 minutes and subjected to a dry heat treatment at 160°C for 2 minutes.

[Formulation 2] (Catalyst for N5-11 manufactured by Sumitomo Chemical Co., Ltd.) For comparison with the present invention, the following treatment was carried out according to a typical conventional method.

First, it was impregnated with a treatment liquid of the following formulation 3, squeezed with a mangle at a squeezing rate of 70%, and then dried at 110° C. for 2 minutes.

[Formulation 3] Sodium monochloroacetate 150g/A caustic soda (flake) 100g/j2Next, neutralization was performed at 40°C for 3 minutes with glacial acetic acid 1g/j', and then,
Soaped with Actinol R-1001g/p at 90°C for 3 minutes.

A processed cloth was obtained for comparison.

The performance of the processed fabrics of the present invention and comparative fabrics was measured and evaluated, and the results are shown in Table 1.

Table 1 As is clear from Table 1, the fabric processed by the method of the present invention had low fluorescent white skin even after 20 washes.

It had excellent stain prevention performance against fluorescent dyes. In addition, the strength of the processed cloth is to the extent that there is no practical problem (700g
above) was maintained. The texture was also flexible.

Example 2 Instead of the fabric to be processed in Example 1 above, a cotton fabric with wire number 40 (warp density 135 lines/inch, weft density 80 lines/inch) was subjected to hair burning, desizing, scouring, and mercerization. A processed fabric of the present invention was obtained in exactly the same manner as in Example 1, except that a colored fabric was used as the fabric to be processed and the following formulation 4 was used in place of formulation 1.

[Formulation 4] Monochloroacetic acid 80g/β caustic soda (flake) 50g/A The performance of the processed fabric and unprocessed fabric of the present invention was measured.

The results are shown in Table 2.

Margin below C] Table 2 From Table 2, it is clear that the processed fabric of the present invention is as follows.

Fluorescent white skin was low even after 20 washes. The hue is.

It had the same color as before washing. In addition, the strength of processed cloth is
The weight was maintained at a level (700 g or more) that caused no practical problems. The texture was also flexible.

(Effects of the Invention) According to the method of the present invention, cellulose-based fibers are provided with excellent fluorescent dye stain prevention performance that hardly causes staining with fluorescent dyes even when washed with fluorescent dye-containing detergents. Moreover, the strength of the fibers can be maintained to a level that poses no problem in practical use.

It is also possible to obtain a soft texture.

Claims (1)

[Claims] (1) Cellulose fibers are treated with a treatment solution containing monochloroacetic acid or sodium monochloroacetate and caustic soda in an amount of 0.05 to 8 mol per cellulose molecule.
% carboxymethylation, and then N-methylol-based cellulose-reactive resin as a solid content of 1 to 1% of the fiber weight.
A method for preventing fluorescent dye staining of cellulose fibers, characterized in that a crosslinking reaction is carried out by adding 4%.